Method of dehydrating uranium tetrafluoride



amazes Patented Dec. 18, 1962 Our invention relates to the processing of uranium tetrafiuoride and more particularly to a method of drying hydrated uranium tetrafluoride.

Uranium tetrafluoride is an intermediate in the preparation of uranium metal both from uranium ore concentrates and from uranium hexafiuoride. UP, is normally prepared from impure uranium ore concentrates by dissolving the ore concentrate in nitric acid, extracting uranium from the resulting solution with an organic solvent, re-extracting the uranium into aqueous solution, denitrating the resulting solution to obtain U reducing the U0 with hydrogen and reacting the resulting U0 with anhydrous hydrogen fluoride. Since the latter steps in this process are carried out at elevated temperatures the product U3 is essentially free of moisture and no further drying is required.

While dry UF suitable for metal preparation is obtained by this process, a disadvantage is presented in the high cost of the numerous process steps. This is particularly the case for uranium scrap material which is only slightly contaminated with impurities,

Less expensive aqueous processes have been developed to eliminate the solvent extraction and high temperature reduction and hydroiiuorination steps. For example, UR, is prepared from impure uranium-bearing material by dissolving the material in hydrochloric acid, filtering the resulting solution to remove insoluble impurities and reacting the solution with a copper sulfate solution, excess hydrofluoric acid and gaseous sulfur dioxide to precipitate UF The U3, is then separated by filtration.

One of the problems presented in the use of this wetprocess UR; is removal of moisture from the precipitate. The UR, precipitate thus obtained is in the form of the hydrate UF- il-l O, and in addition the precipitate contains a substantial quantity of free moisture. The free moisture is readily removed by heating the precipitate to a temperature of approximately 115 C. in a conventional steam-heated dryer. Removal of the water of hydration, however, requires much higher temperatures and careful control of heating conditions to prevent the formation of excessive amounts of uranium oxides and uranyl fluoride. Expensive high-temperature calciners or furnaces have been required for this operation, and considerable labor has been expended in materials handling. For use in the preparation of uranium metal, U1 with a moisture content of less than about 0.2 weight percent is desired.

in addition to drying of the precipitated U1 blending of this U1 with U1 produced by other methods is frequently desired. For example, where UR, for metal preparation is produced by hydrogen reduction of UF and smaller amounts of U1 are concurrently produced from metal-fabrication scrap by the aqueous process described above, blending of the UR, from the two sources is advantageous in producing a uniform metal product. Owing to differences in chemical composition and physical properties such as density and particle size the two types of HE would otherwise produce metal of varying quality.

It is, therefore, an object of our invention to provide a method of drying UF Another object is to provide a method of dehydrating 'UF -%H O.

Another object is to provide a method of blending aqueous-precipitated U1 with UR; prepared by reacting UP with hydrogen.

Other objects and advantages of our invention will be apparent from the following detailed description and claims appended hereto.

In accordance with our invention, moisture-containing UR, is dried by reacting gaseous UP and hydrogen under such conditions as to produce UR, and dispersing said moisture-containing UR, into the resulting UP hydrogen reaction mass. Aqueous-precipitated UR; is readily dried by this means without interfering in any way with the reaction of UF and hydrogen. The dried UR; product obtained in this manner is a uniform blend of the aqueous-precipitated UR; and the UR, produced by the reaction of UP and hydrogen.

We have found that UR; may be dried in an operating Ul -hydrogen reactor without detrimental effect to the UP reduction process or to the quality of the product UF Although it would be expected that UF might react with the water vapor from the hydrated UF to produce uranyl fluoride and uranium oxides, the hydrogen and HF cit-gas present from the reaction of UP with hydrogen apparently act to prevent formation of excessive amounts of these compounds.

Our invention is applicable to drying UR, containing up to approximately 5 weight percent total water. It is preferred, however, to remove the free moisture from precipitated UR, by heating the precipitate to a temperature of about C. for a period of approximately 30 minutes prior to treating the U11 by the method of our invention. Precipitated UP] partially dried in this manner usually contains 3 to 4 percent moisture in the form of water of hydration.

Although the method of our invention is not to be understood as limited to a particular apparatus, this method is particularly applicable to UP -hydrogen reactors of the hot-wall type. This type of reactor comprises an externally heated, vertically disposed, elongated metallic cylinder provided with inlets at the top for introducing gaseous UF and hydrogen and a container at the bottom for collecting product U1 This type of reactor is normally employed for preparation of UR, from UP of natural uranium isotopic composition or UF slightly enriched, i.e., up to 5 percent, in fissionable uranium 235. In the operation of this type of reactor, the reactor Walls are heated to a temperature of at least 550 C. and preferably 630 C., and gaseous UP and hydrogen are concurrently and continuously introduced. The UF and hydrogen react exothermically to produce a maximum temperature of about 850 C. to 900 C. within the reactor. The reaction proceeds smoothly, and a relatively constant temperature is maintained. The reactor pressure is regulated to slightly above atmospheric pressure, in the range of 0 to 10 pounds per square inch gauge. Excess hydrogen is required for complete conversion of UF to UF with approximately 30 percent being preferred. Greater proportions of hydrogen may result in a low-density product unsuitable for preparation of uranium metal.

The moisture-containing UR, is introduced as dispersed particles into the UP -hydrogen reaction mass along with these reagents. In order to provide for uniform dispersion of the moisture-containing UR; it is preferred to continuously introduce this material by entraining it in the influent hydrogen gas stream. The UR, may be entrained by continuously conveying the UR, by means of a conventional auger into a cylindrical mixing chamber into which the hydrogen gas stream is tangentially introduced to obtain turbulent flow. The size of the dispersed Q cue-precipitated UF-%H- O may be employed without pulverization.

Although the proportion of moisture-containing UR, supplied to the UP -hydrogen reaction mass is not critical, it is preferred to supply hydrated UR; at a rate sufficient to provide a hydrated-source content in the resulting blend of to weight percent. For greater proportions of hydrated UR; additional external heat may be required. The blended UR; product is recovered by separating the U1 from the emuent gas stream. A major proportion of the UR; falls out of the stream and may be collected by providing a container at the bottom of the reactor. The remainder of the UR; may be separated by conventional filtration.

The resulting blended UR; meets normal specifications for uranium metal preparation, that is, an ammonium oxalate insoluble (uranium oxides) content below 2 weight percent, a uranyl fluoride content from 0.5 to 2.0 weight percent, a moisture content under approximately 0.2 weight percent and a tap density above 3.3 grams per cubic centimeter. The blended UR; may be converted to uranium metal by reduction with magnesium or calcium, and any of the previously known techniques may be employed for this reaction.

In processing UR; enriched in fissionable uranium 235 it is preferred to blend the moisture-containing UR; with UF having the same degree of isotopic enrichment in order to avoid dilution of costly enriched material. However, blendingof materials of (littering isotopic enrichments can be conveniently accomplished by this means when it is desired to do so.

Our invention is further illustrated by the following specific examples.

EXAMPLE I Hydrated UF -%H O prepared by aqueous precipitation was dried and blended with UR; produced by hydrogen reduction of UF in a series of pilot-plant scale runs. The initial moisture content of the hydrated U1 was ap proximately three weight percent. The hydrated UF was fed into the top of a UF -hydmgen reactor from a closed hopper provided with a variable speed discharge screw. The UP -hydrogen reactor comprised a cylinder 20 feet long and 15 inches in diameter, the cylinder being comprised of the nickel-base alloy available commercially under the trade name Monel. UP was fed into the top of the reactor at a pressure of 1 p.s.i. gauge and a rate of 13 pounds per minute. Hydrogen percent in excess of the stoichiometric amount required to react with the UP was concurrently fed into the top of the reactor through a separate nozzle. The reactor walls were heated externally to a temperature of 630 C. by means of external ribbon-element resistance heaters. The hydrated UR; was fed at varying rates for each of a series of runs to produce blends of varying compositions. The resulting UF blend was collected from the reactor discharge in each run and analyzed to determine water content, tap density, UO F content and ammonium oxalate insoluble (uranium oxides) content. Further details and results obtained may be seen by reference to the following table.

It may be seen from the above table that the moisture content of the blended UR; was reduced to the desired level in each case. The blended UR; was well within normal metal-preparation specifications with respect to tap density, UO F content and ammonium oxalate insoluble content.

EXAMPLE II Blended U1 produced in each of the runs described in Example I was subjected to reduction with magnesium in order to determine further the suitability of this material for metal preparation. For each of the first three runs batch reductions were conducted in the following manner: The UR; was blended with 4 percent excess of the stoichiometric amount of magnesium required to reduce the uranium, and a cylindrical steel vessel 18 inches high, 7.25 inches in inner diameter, and lined with a magnesium fluoride liner tapered from 1.25 inches thickness at the bottom to 0.75 inch at the top was filled with the resulting blend. The reactor was sealed and heated in an induc tion furnace until the mixture ignited. After cooling the reactor was broken open and the resulting uranium derby was removed. For run 4 the same procedure was follower except that a larger reactor was used (42 inches high, 15.375 inches inner diameter at the top and 14.250 inches inner diameter at the bottom). The results ob tained may be seen by reference to the following table.

Table II REDUCTION OF BLENDED U73 Percent Number of Avcra ge Average U3; from Run N0. hydratsdreductions yield firing time source UR, carried out (percent) (minutes) 20 13 97. 9 123 33 8 96. t) 28 i 98. 6 143 18 (l 98. 1 301 The uranium derbies produced as described above separated cleanly from reaction-product slag and were suitable for metal fabrication, both with respect to chemical impurity content and physical properties.

vIt: maybe seen from the above table that the blended UR; prepared by the method of our invention may be readily reduced to high-quality metal at high yields.

The above examples are merely illustrative and are not to be construed as limiting in any manner the scope of our invention, which is limited only as indicated in the appended claims.

Having thus described our invention, We claim:

1. The method of dehydrating UF -%H O and blending the resulting UR; with U3; produced by reacting UF and hydrogen which comprises continuously introducing said UP and said hydrogen into the top of a vertically disposed reaction zone under such conditions as to effect a reaction whereby U35 is formed, continuously dispersing said UF A1H O into the top of said reaction zone and recovering the resulting blended UPI 2. The method of claim 2 in which said UF AH O is dispersed in said reaction zone at a rate sufiicient to provide a proportion oftrom 5 to 25 weight percent of the total resulting blended U1 V 3. The method of dehydrating UF -%H O and blend ing the resulting U1 with U1 produced by reacting UF and hydrogen which comprises continuously introducing a stream of UF and a stream of hydrogen containing said UF AH O dispersed therein into the top of a vertically disposed reaction zone, said reaction zone being heated to' to 5 weight percent total water and blending the resulting.

UR; with UR; produced by reacting HE and hydrogen which comprises continuously contacting gaseous UP 7 and gaseous hydrogen in a reaction zone under such' conditions as to effect a reaction whereby UR; is formed, FOREIGN PATENTS continuously dispersing said water-containing UF into 821,957 Great Britain Oct 14 1959 the resulting reaction mass and recovering the resulting blended UR OTHER REFERENCES References flied in the file of this P 5 Harrington and Rueble: Uranium Production Tech- UNITED STATES PATENTS y, pp- 479-483 9 9)- 2,907,629 Smiley et a1. Oct. 6, 1959 

4. THE METHOD OF DRYING HYDRATED UF4 CONTAINING UP TO 5 WEIGHT PERCENT TOTAL WATER AND BLENDING THE RESULTING UF4 WITH UF4 PRODUCED BY REACTING UF6 AND HYDROGEN WHICH COMPRISES CONTINUOUSLY CONTACTING GASEOUS UF6 AND GASEOUS HYDROGEN IN A REACTION ZONE UNDER SUCH CONDITIONS AS TO EFFECT A REACTION WHEREBY UF4 IF FORMED, CONTINUOUSLY DISPERSING SAID WATER-CONTAINING UF4 INTO THE RESULTING REACTION MASS AND RECOVERING THE RESULTING BLENDED UF4. 